Treatment of hydrocarbon oils



July 17, 1934;

J. c. MORRLL Filed Feb. 21, V1930 TREATMENT HYDROCARBON OILS WW i Jacyue /llarrell this stage or "preferably Patented .my 11, 1934 UNITED A'sra'llizs i l 1,966,455 Y TREATMENT F HYDBOCABBON OILS Jacque C; -Morrell, Chicago, Ill., assignor to Universal Oil Products Comm, chimo, my

a corporation of South Dakota Application` ,February 21, 1930, Serial No. 430,399 2 Claims. (Cl. 1915-6q 2) 'Ihis invention relates to a process for the treatment of hydrocarbon oils, and refers more particularly to a process for the hydrogenation of oils at elevated temperatures.

- 6 Among the obiects of the process is to increase the yield of the lower boiling products made by the thermal decomposition or cracking of higher boiling oils. In the operation of the process of my inven- 10 tion, flnelydivided metals are introduced similitaneously with a basic material or alkali in those portions of the cracking system where the oil is a nonvaporized product of the process.

For a clearer understanding of the invention,

`* reference is had to the accompanying diagrammatic drawing, which bears appropriate legendsl and wherein the ,cracking zone is intended to ,ex--

` emplify a vaporseparating zone, such as a re,-

action or flash chamber, or the like.

2o In the Yspecific embodiment of the present invention, the .hydrocarbons are treated in. the liquid state, with especial application to the hydrogenation "of the non-vaporized residue from the reaction and flash `chamber of the cracking process.- For example, the invention may be used in a process well known in the art wherein oil is heated in a continuous coiland discharged in a reaction chamber from which is withdrawn the vaporous products resulting from the distillatel and cracking and a non-vaporizedv residue. The

residue from the reaction chamber maybe treated according to the present invention by passing same through an insulated pipe or vessel, introducing the finely divided metal and alkali at by thelapplication of external heat toe the residue leaving the reaction chamber while in the presence of alkali and thel finely divided metal.

In one mode of operation the non-vaporized residue is discharged from the reaction chamber under pressure and -is vaporized by its self-contained heat in a vessel at lower pressure, the amount of vaporizationdepending upon the temperature, average boiling vpoint of the residue, and the pressure within the'low pressure vessel or iiash chamber.- This flashed residue mayzbe likewise treated by heating in the presence of finely divided metals and alkali. G The non-vaporized hydrocarbon oils and basic materials or alkali or substances giving an. alkaline reaction are mixed with finely divided metals which react with the alkali at elevated temperatures to produce hydrogen. Preferably, the alkali is introduced into the oil in aqueous solution. u 'As examples of alkalies, the hydroxides of Sodium, potassium, ammonium, calcium. barium, strontium, and/or the corresponding oxides and carbonates may -be used. The alkali reacts with the' finely divided metal producing hydrogen in situ. This hydrogen is more active than ordinary o0 molecular hydrogen and is sometimes spoken of as being in the nascent state, reacts with the chemically unsaturated portions of the oil as well as with sulfur compounds, saturating in part the pitchy and unsaturated or olenic hydrocarbons o5 and reducing some of the higher sulfur compounds to hydrogen sulfide which may readily 'be removed from the final products.

As examples -of metals, I may use sodium, potassium, calcium, magnesium, zinc, aiumin iron, tin, and others, including alloys and amalgains, preferably the metals which are electropositive to lwdrogen, i. e., are above hydrogen in the electromotive series, and whichliberate hydrogen from steam. TheV oxides or metals formed by the reaction with steam have some catalytic action in promoting the hydrogenation and desuli'urization` as'well as assisting in the cracking. -The use of finely divided metals has an additional advantage in that the finer the so metal the'grea'ter the surface exposure and consequently the greater the'velocity or rate of-reaction.

In addition to the above I may also add molecular hydrogen tothe materials undergoing reaction in order to assist in the reaction, or I may add gases containing hydrogen lsuch as gases from oil cracking, coke ovengas, producer gas. natural gas, et cetera.

In operating the process of the invention I may no make use of anyv conventional apparatus or equipment suitable for cracking, but preferably I make use of a cracking system consisting of heating tubes or elongated pipe orheating coil in combination with a reaction chamber, dephlegmator or fractionating Ameans and the auxiliary cooling, condensing, and collecting devices. In the '4 operation of the process I preferably return the reflux or distillates condensed in the dephlegmat- ,ing or fractionating means to the heating equipma ment for reconversion. Auxiliary heating equipment may be used to heat the mixture ofnonvaporized residue, metals and alkalies. y Preferably, the oil is heated to a cracking tem'- perature, although my invention contemplates m5 operating the process at lower `temperatures also.

Preferably the process is operated at superatmospheric pressure, and may in some cases also be operated at atmospheric, reduced or sub-atlnospheric pressures. Preferably I make use o! no superatmo'spheric pressures ranging from 75 pounds to 3000 pounds, more or less, and at temperatures of from approximately 400 to 1400 l".

As an example of the process;y a 241-26 API. gravity Mid-continent topped crude when sub- Ajected to a. cracking temperature o! approximately 930 F. and a pressure of approximately 1000 pounds shows an approximate yield ot gasoline ci nity percent, in addition to approximately fortyiive percent of liquid fuel oil of good. viscosity l and very low sludge or` coke content. Approxi- 0.1 percent.

mately tive percent of coke and gas are also produced. The suliul'v content of the gasoline produced, which would normally be approximately 0.25 percent, may be reduced vto approximatelyl The above example is illustrative land is not?A to be construed as a limitation upon my invention.

I claim as my invention: Y l. A process i'or treating the residuum formed in the pressure cracking ci hydrocarbon oils which comprises removing such residuum from the t cracking process and mixing therewith. while the residuum is still in highly heated 'condition, an alkaline material and n metal capable oi' reacting witheach other to form suilicient nascent hydrogen to saturate unsaturated hydrocarbons, subjecting the resultant mixture to 'hydrcgenating conditions of temperature and pressure adequate to form lower boiling hydrocarbons and using the heatclel'ivefl from the cracking and present in the reeiduum toward obtaining the hydrogenating temperature.

2. A process iortreating the residuum formed in the pres'surecracking of hydrocarbon oils j .which comprises removing such residuum from the vcracking process and mixing therewith, while the residuum is still in highly heated condition.

*an alkaline material and a metal capable oi reals f 

